WO2021099898A1 - Granulés céramiques à revêtement photocatalytique et leur procédé de fabrication - Google Patents

Granulés céramiques à revêtement photocatalytique et leur procédé de fabrication Download PDF

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Publication number
WO2021099898A1
WO2021099898A1 PCT/IB2020/060671 IB2020060671W WO2021099898A1 WO 2021099898 A1 WO2021099898 A1 WO 2021099898A1 IB 2020060671 W IB2020060671 W IB 2020060671W WO 2021099898 A1 WO2021099898 A1 WO 2021099898A1
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WIPO (PCT)
Prior art keywords
granules
photocatalytic
ceramic granules
particles
coated
Prior art date
Application number
PCT/IB2020/060671
Other languages
English (en)
Inventor
Taisiya SKORINA
Rebecca L. A. EVERMAN
Jean A. Tangeman
Eric J. VANBRUGGEN
Kenton D. Budd
Rachael A. T. Gould
Robert P. Brown
Lara K. N. UGHETTA
Jonathan A. HUBIN
Zachary M. SCHAEFFER
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3M Innovative Properties Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 3M Innovative Properties Company filed Critical 3M Innovative Properties Company
Priority to US17/755,296 priority Critical patent/US20220403659A1/en
Priority to EP20821064.1A priority patent/EP4062006B1/fr
Priority to CN202080075632.8A priority patent/CN114641598A/zh
Publication of WO2021099898A1 publication Critical patent/WO2021099898A1/fr
Priority to US18/408,421 priority patent/US20240141649A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/87—Ceramics
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
    • E04D7/00—Roof covering exclusively consisting of sealing masses applied in situ; Gravelling of flat roofs
    • E04D7/005—Roof covering exclusively consisting of sealing masses applied in situ; Gravelling of flat roofs characterised by loose or embedded gravel or granules as an outer protection of the roof covering
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/4584—Coating or impregnating of particulate or fibrous ceramic material
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00586—Roofing materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/2038—Resistance against physical degradation
    • C04B2111/2061—Materials containing photocatalysts, e.g. TiO2, for avoiding staining by air pollutants or the like
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/80—Optical properties, e.g. transparency or reflexibility
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
    • E04D1/00—Roof covering by making use of tiles, slates, shingles, or other small roofing elements
    • E04D2001/005—Roof covering by making use of tiles, slates, shingles, or other small roofing elements the roofing elements having a granulated surface

Definitions

  • titania-based photocatalytic coatings used on roofing granules to provide, e.g., self-cleaning and smog-reducing functionality.
  • An exemplary formula includes nano-sized titania (anatase-rutile mixture) embedded in an inorganic binder.
  • photo-induced redox chemistry of TiO 2 eliminates soiling and air pollutants adsorbed on the granule surface, including organic compounds and atmospheric NO x .
  • photocatalytic oxidation enables the removal of NO x from the air through conversion to nonvolatile [NO 3 -]-containing compounds.
  • the disclosure provides a plurality of coated ceramic granules including: base ceramic granules, each having an outer surface; and a photocatalytic coating disposed on the outer surface, wherein the photocatalytic coating includes an inorganic binder and a plurality of photocatalytic particles selected from TiO 2 , ZnO, Ti(OH) 4 , doped derivatives thereof, and combinations thereof, wherein the photocatalytic particles have a surface area per weight of the particles of no more than 30 square meters per gram (m 2 /g); and wherein the coated ceramic granules have a Total Solar Reflectance of at least 0.7.
  • a method of making photocatalytic coated ceramic granules that include base ceramic granules, each having an outer surface, and a photocatalytic coating disposed on the outer surface, is provided.
  • the method includes: providing a coatable composition containing an inorganic binder and a plurality of photocatalytic particles selected from TiO 2 , ZnO, Ti(OH) 4 , doped derivatives thereof, and combinations thereof, wherein the photocatalytic particles have a surface area per weight of the particles of no more than 30 square meters per gram (m 2 /g); applying the coatable composition to uncoated base ceramic granules to form intermediate coated granules; and heating the intermediate coated granules at a temperature of at least 700°C to produce the photocatalytic coated ceramic granules having a Total Solar Reflectance (TSR) of at least 0.7.
  • TSR Total Solar Reflectance
  • the phrase “consisting essentially of” indicates that the listed elements are required or mandatory, but that other elements are optional and may or may not be present depending upon whether or not they materially affect the activity or action of the listed elements.
  • the words “preferred” and “preferably” refer to embodiments of the disclosure that may afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances.
  • the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the disclosure.
  • terms such as “a,” “an,” and “the” are not intended to refer to only a singular entity, but include the general class of which a specific example may be used for illustration.
  • phrases “a,” “an,” and “the” are used interchangeably with the phrases “at least one” and “one or more.”
  • the phrases “at least one of” and “comprises at least one of” followed by a list refers to any one of the items in the list and any combination of two or more items in the list.
  • the term “or” is generally employed in its usual sense including “and/or” unless the content clearly dictates otherwise.
  • the term “and/or” means one or all of the listed elements or a combination of any two or more of the listed elements.
  • the present disclosure provides coated ceramic granules.
  • Such ceramic granules include a photocatalytic coating disposed thereon.
  • the coated granules when utilized in building materials, are capable of significantly reducing and/or preventing solar and/or environmental degradation on the resultant building materials.
  • the disclosure provides a plurality of coated ceramic granules including: base ceramic granules, each having an outer surface; and a photocatalytic coating disposed on the outer surface, wherein the photocatalytic coating includes an inorganic binder (i.e., a “photocatalytic coating binder”) and a plurality of photocatalytic particles selected from TiO 2 , ZnO, Ti(OH) 4 , doped derivatives thereof, and combinations thereof, wherein the photocatalytic particles have a surface area per weight of the particles of no more than 30 square meters per gram (m 2 /g).
  • an inorganic binder i.e., a “photocatalytic coating binder”
  • a plurality of photocatalytic particles selected from TiO 2 , ZnO, Ti(OH) 4 , doped derivatives thereof, and combinations thereof, wherein the photocatalytic particles have a surface area per weight of the particles of no more than 30 square meters per gram (m 2 /g).
  • the coated ceramic granules have a Total Solar Reflectance (TSR) (as determined by the Total Solar Reflectance Test described in the Examples Section) of at least 0.7, and in certain embodiments, at least 0.75, or at least 0.8.
  • TSR Total Solar Reflectance
  • the photocatalytic coating includes an inorganic binder and a plurality of photocatalytic particles.
  • the photocatalytic particles are sufficiently distributed throughout the coating so that at least a portion of some of the photocatalytic particles are exposed on the surface of the coating.
  • Photocatalytic particles upon activation or exposure to sunlight, establish both oxidation and reduction sites. These sites are capable of preventing or inhibiting the growth of algae on the granules and eliminating air pollutants adsorbed on the granule surface, including organic compounds and atmospheric NO x .
  • the function of the inorganic binder is to adhere the coating to the base ceramic granules.
  • the coated granules of the present disclosure are ideally suited for use in various applications in building materials.
  • the coated granules are well suited for use as roofing granules.
  • the coated granules may be applied to warm bituminous coated shingle base material of a felt or fiberglass.
  • the coated granules of the present disclosure may be used in various interior and exterior products such as, for example, roofing materials, concrete and cement based materials, plasters, asphalts, ceramics, stucco, grout, plastics, and glass.
  • Additional examples include pool surfaces, wall coverings, siding materials, flooring, filtration systems, cooling towers, buoys, seawalls, retaining walls, docks, and canals so as to provide a surface capable of remaining free from discoloration.
  • the photocatalytic coating When the photocatalytic coating is utilized to coat roofing granules, the granules reduce or prevent transmission of light, particularly ultraviolet light, from reaching the underlying asphalt. Exposure of asphalts to UV light, especially light in the range from approximately 290 nm to 430 nm, is known to accelerate undesirable weathering of the asphalt resulting in water solubility, loss of thermoplasticity, cracking, and ultimately failure of the shingle.
  • the photocatalytic coatings of the present disclosure are capable of reducing the UV light transmittance to 2% or less, or to 1% or less.
  • the photocatalytic coatings of the coated ceramic granules described herein demonstrate photocatalytic activity, measured as described in the Examples Section, of greater than 10 X 10 5 , or greater than 100 X 10 5 in relative TPA activity units (defined in the Example Section).
  • Base Ceramic Granules Base ceramic granules include ceramic particles.
  • ceramic refers to a solid material comprising an inorganic compound of metal, non-metal, or metalloid atoms primarily held in ionic and covalent bonds. It is often an oxide, nitride, or carbide (e.g., a silicon oxide, boron oxide, phosphorous oxide), and may include at least one of a carbon or a nitrogen, in at least one of an amorphous, crystalline, or glass-ceramic form. Ceramic materials are brittle, hard, strong in compression, and weak in shearing and tension. They withstand chemical erosion that occurs in other materials subjected to acidic or caustic environments. Typical base ceramic granules of the present disclosure have a high Total Solar Reflectance (TSR).
  • TSR Total Solar Reflectance
  • the base ceramic granules have a TSR (as determined by the Total Solar Reflectance Test described in the Examples Section) of at least 0.7, and in certain embodiments, at least 0.75, or at least 0.8.
  • the base ceramic granules may have a core-shell structure.
  • the base ceramic granules include ceramic particles bound together with or without an inorganic binder (no core-shell structure).
  • the ceramic granules that do not have a core-shell structure may be sintered (e.g., at a temperature in a range of 650°C to 900°C) with or without an inorganic binder.
  • Base ceramic granules that include an inorganic binder i.e., a “base granule binder” distinct from the photocatalytic coating binder, although these binders could be compositionally the same or similar
  • Base ceramic granules that include an inorganic binder optionally include a hardener.
  • Examples of such granules that include an inorganic binder are disclosed, for example, in International Publication Nos. WO 2017/200844, WO 2018/234942 and WO 2018/234943 (all to 3M Innovative Properties Company).
  • the ceramic granules that have a core-shell structure may include an inorganic (e.g., ceramic) core having an outer surface and a shell on and surrounding the outer surface.
  • the shell includes ceramic particles bound together with an inorganic binder (a base granule binder).
  • the inorganic core of the core-shell granules includes a solid ceramic core.
  • solid ceramic core refers to a ceramic that is substantially solid (i.e., has no more than 10 percent porosity, based on the total volume of the core).
  • the inorganic core includes at least one of a silicate (e.g., silicate rock) (e.g., aluminosilicate (including aluminosilicate rock) and alkali aluminosilicate (including alkali aluminosilicate rock)), aluminate (including aluminate rock) (e.g., bauxite), or silica.
  • a silicate e.g., silicate rock
  • aluminosilicate including aluminosilicate rock
  • alkali aluminosilicate rock alkali aluminosilicate rock
  • aluminate including aluminate rock
  • silica e.g., silica
  • the inorganic core is at least one of a crystalline, a glass, or a glass-ceramic.
  • Such materials can be obtained from conventional roofing granule sources known in the art. Further crystalline, glass, or glass-ceramic materials can
  • the base granule itself (in the non-core-shell structure) or shell of a base granule includes ceramic particles bound together with an inorganic binder.
  • the ceramic particles include at least one component with Total Solar Reflectance (as determined by the Total Solar Reflectance Test described in the Examples Section) of at least 0.7, and in certain embodiments, at least 0.75, or at least 0.8.
  • Such exemplary ceramic particles include aluminum hydroxide, a metal or metalloid oxide (e.g., silica (e.g., crystoballite, quartz, etc.), an aluminate (e.g., alumina, mullite, etc.), an aluminosilicate (e.g., feldspar, clay, etc.), a titanate (e.g., titania), and zirconia), a silicate glass (e.g., soda-lime-silica glass, a borosilicate glass), porcelain, calcite, or marble.
  • the ceramic particles include minerals, such as feldspars or nepheline syenite.
  • the inorganic binder of the base granule (which may be throughout the base granule or in a shell of a core-shell base granule) includes a reaction product of at least an alkali silicate and a hardener.
  • the inorganic binder of the base granule (which may be throughout the base granule or in a shell of a core-shell base granule) includes a reaction product of at least an alkali silicate and a hardener and further an alkali silicate itself.
  • the shell of the core-shell granules includes at least first and second concentric layers, wherein the first concentric shell layer is closer to the core than the second concentric shell layer, wherein the first concentric shell layer includes ceramic particles bound together with an inorganic binder.
  • the inorganic binder of the first concentric shell layer includes a reaction product of at least an alkali silicate and hardener (in some embodiments, further including alkali silicate itself).
  • a ”hardener refers to a material that initiates and/or enhances hardening of an aqueous silicate solution; hardening implies polycondensation of dissolved silica into three- dimensional Si-O-Si(Al, P, B) bond network and/or crystallization of new phases; in some embodiments, the granules comprise excess hardener.
  • the hardener is amorphous.
  • amorphous refers to a material that lacks any long-range crystal structure, as determined by X-ray diffraction.
  • hardeners include aluminum phosphate, an aluminosilicate, a cryolite, a calcium salt, and a calcium silicate.
  • exemplary aluminosilicate compounds include clay having the formula Al 2 Si 2 O 5 (OH) 4 , kaolin having the formula Al 2 O 3 ⁇ 2Si 2 O 2 ⁇ 2H 2 O.
  • Suitable alkali silicates include cesium silicate, lithium silicate, a potassium silicate, or a sodium silicate.
  • Exemplary alkali silicates are commercially available, for example, from PQ Corporation, Malvern, PA.
  • the inorganic binder of the base granule further includes reaction product of at least an alkali silicate and an amorphous aluminosilicate hardener.
  • the ceramic particles are present in an amount of greater than 50 percent by weight (wt-%) of the respective granule. In some embodiments, this amount is greater than 55 wt-%, greater than 60 wt-%, greater than 65 wt-%, greater than 70 wt-%, greater than 75 wt-%, greater than 80 wt-%, or even greater than 85 wt-%, based on the total weight of each granule.
  • the ceramic particles are present in a range of greater than 50 wt-% and up to 85 wt-%, or even greater than 60 wt-% and up to 85 wt-%, based on the total weight of each granule.
  • each granule has a total porosity in a range of greater than 0 and up to 60 volume percent (vol-%), based on the total volume of the respective granule.
  • the total porosity of such granules is in a range of 5 vol-% to 60 vol-%, 20 vol-% to 60 vol-%, 5 vol-% to 50 vol-%, 20 vol-% to 50 vol-%, or even 20 vol-% to 40 vol-%.
  • Such base ceramic granules are disclosed, for example, in International Publication No. WO 2017/200844 (3M Innovative Properties Company).
  • the ceramic particles are present in an amount of greater than 50 percent by weight (wt-%) of the shell of the respective granule, based on the total weight of the shell of the respective granule.
  • this amount is greater than 55 wt-%, greater than 60 wt-%, greater than 65 wt-%, greater than 70 wt-%, greater than 75 wt-%, greater than 80 wt-%, or even greater than 85 wt-%.
  • the ceramic particles are present in a range of greater than 50 wt-% and up to 85 wt-%, or even greater than 60 wt-% and up to 85 wt-%.
  • the shell of each granule has a total porosity in a range of greater than 0 and up to 60 volume percent (vol-%), based on the total volume of the shell of the respective granule.
  • the total porosity of the shell is in a range of 5 to 60 vol-%, 20 to 60 vol-%, 5 to 50 vol-%, 20 to 50 vol-%, or even 20 to 40 vol- %.
  • the shell of each granule has a volume of at least 40 vol-%, based on the total volume of the respective granule.
  • the shell of each granule has a volume of greater than 45 vol-%, greater than 50 vol-%, greater than 55 vol-%, greater than 60 vol-%, greater than 65 vol- %, greater than 70 vol-%, greater than 75 vol-%, greater than 80 vol-%, or even greater than 85 vol-%. In some embodiments, the shell of each granule has a volume in a range of greater than 50 vol-% and up to 85 vol-%, or even greater than 60 vol-% and up to 85 vol-%.
  • Such ceramic core- shell particles are disclosed, for example, in International Publication No. WO 2018/234942 (3M Innovative Properties Company).
  • the base ceramic granules that include a core-shell structure in which the shell includes at least first and second concentric layers, wherein the first concentric shell layer is closer to the core than the second concentric shell layer, wherein the first concentric shell layer includes first ceramic particles bound together with a first inorganic binder, the second layer includes a second inorganic binder and optionally second ceramic particles. If present, the second ceramic particles are bound together with the second inorganic binder, wherein the second inorganic binder includes a reaction product of at least an alkali silicate and a hardener (in some embodiments further comprising alkali silicate itself).
  • the first ceramic particles are present in a first weight percent with respect to the total weight of the first layer and the second ceramic particles are present in the second layer of the same granule in a second weight percent with respect to the total weight of the second layer, wherein for a given granule, the first weight percent is greater than the second weight percent, wherein the shell of each granule collectively has a volume of at least 40 vol-% (in some embodiments, greater than 45 vol-%, greater than 50 vol-%, greater than 55 vol-%, greater than 60 vol-%, greater than 65 vol-%, greater than 70 vol-%, greater than 75 vol-%, greater than 80 vol-%, or even greater than greater than 85 vol-%; in some embodiments, in a range of greater than 50 vol-% and up to 85 vol-%, or even greater than 60 vol-% and up to 85 vol-%), based on the total volume of the respective granule.
  • the core has a diameter of at least 200 micrometers (i.e., microns).
  • the shell has a thickness of at least 50 micrometers.
  • the reflective shell coating of the base ceramic core-shell particles is up to 400 microns thick.
  • the ceramic particles of each ceramic base granule include no more than 10 wt-% TiO 2 , and/or no more than 10 wt-% Al 2 O 3 , based on the total weight of either the core or base ceramic granule for the respective core or base ceramic granule.
  • the photocatalytic coating includes an inorganic binder (i.e., a photocatalytic coating binder distinct from the binder(s) of the base ceramic granules, although these binders could be compositionally the same or similar) and a plurality of photocatalytic particles selected from TiO 2 , ZnO, Ti(OH) 4 , doped derivatives thereof, and combinations thereof.
  • Photocatalytic particles suitable for use on the base ceramic granules include transition metal photocatalysts such as TiO 2 , ZnO, Ti(OH) 4 , doped derivatives thereof (e.g., doped with nitrogen), or combinations thereof.
  • Preferred photocatalysts are particles of TiO 2 (e.g., anatase TiO 2 ). Characteristics utilized to distinguish particles from one another include the mean particle size (primary particle size) and the surface area per weight of particles. The mean particle size may be determined by laser diffraction as described in the Examples Section. The surface area per weight of particles may be determined through nitrogen adsorption as described in the Examples Section. In certain embodiments, the photocatalytic particles of the present disclosure have a mean particle size of at least 100 nanometers (nm), and in certain embodiments, at least 200 nm, at least 500 nm, or at least 1000 nm.
  • nm nanometers
  • the photocatalytic particles of the present disclosure have a mean particle size of up to 3000 nm, and in certain embodiments, up to 2000 nm, or up to 1000 nm. In certain embodiments, the photocatalytic particles of the present disclosure have a surface area per weight of the particles of no more than 30 square meters per gram (m 2 /g), and in certain embodiments, no more than 25 m 2 /g, no more than 20 m 2 /g, no more than 15 m 2 /g, no more than 14 m 2 /g, no more than 13 m 2 /g, no more than 12 m 2 /g, no more than 11 m 2 /g, or no more than 10 m 2 /g.
  • m 2 /g square meters per gram
  • the photocatalytic particles of the present disclosure have a surface area per weight of the particles of at least 1 m 2 /g.
  • Such surface areas are presented in terms of Brunauer–Emmett–Teller (BET) specific surface area (SSA) (surface area per mass), which can be determined by Nitrogen absorption, as described in the Examples Section.
  • BET Brunauer–Emmett–Teller
  • SSA specific surface area
  • the recited surface areas are of the photocatalytic particles prior to incorporation into the granules. Upon incorporation into the granules, and processing, such surface area would typically be the same or reduced.
  • the total surface area the particles is a large fraction of that of the overall granules, and the majority of the surface remains exposed and not covered by the binder. In most cases, the surface area of the photocatalytic particles will decrease somewhat due to granule processing, but the change is small under conditions that maintain desirable photocatalytic activity.
  • the surface area of the photocatalytic particles can also be calculated from images of the photocatalytic particles (including within the final granules), based on approximate spherical geometry.
  • TEM Transmission Electron Microscopy
  • SEM Scanning Electron Microscopy
  • the inorganic binder of the photocatalytic coating primarily includes an alkali metal silicate binding agent.
  • Alkali metal silicate binding agents typically include those selected from the group consisting of lithium silicate, potassium silicate, sodium silicate, and combinations thereof.
  • alkali silicate binding agents include those selected from the group consisting of lithium silicate, potassium silicate, and combinations thereof.
  • the alkali metal silicate is generally designated as M 2 O:SiO 2 , where M is lithium, potassium, or sodium. In certain embodiments, M is lithium or potassium.
  • the weight ratio of SiO 2 to M 2 O typically ranges from 1.4:1 to 3.75:1, and in certain embodiments from 2.1:1 to 3.22:1.
  • the coating includes a plurality of photocatalytic particles in an amount of at least 45 percent by weight (wt-%), or at least 60 wt-%, based on the total weight of the coating. In certain embodiments, the coating includes a plurality of photocatalytic particles in an amount of up to 95 wt-%, or up to 80 wt-%, based on the total weight of the coating.
  • the photocatalytic coating includes an inorganic binder in an amount of at least 5 wt-%, at least 10 wt-%, at least 15 wt-%, or at least 20 wt-%, based on the total weight of the coating. In certain embodiments, the photocatalytic coating includes an inorganic binder in an amount of up to 55 wt-%, up to 50 wt-%, up to 45 wt-%, or up to 40 wt-%, based on the total weight of the coating.
  • the photocatalytic coating includes a crosslinker, which may be the same as a hardener of the base granule.
  • Exemplary crosslinkers include boric acid, a borate, a silicate (e.g., potassium fluorosilicate), a fluoroaluminate, an aluminosilicate, or combinations thereof.
  • exemplary aluminosilicate compounds include clay having the formula Al 2 Si 2 O 5 (OH) 4 , kaolin having the formula Al 2 O 3 ⁇ 2Si 2 O 2 ⁇ 2H 2 O.
  • Various combinations of crosslinkers may be included.
  • the photocatalytic coating includes a crosslinker in an amount of at least 2 wt-%, based on the total weight of the coating.
  • the photocatalytic coating includes a crosslinker in an amount of up to 10 wt-%, based on the total weight of the coating.
  • coating of the present disclosure may include additives, such as photocatalytic activity enhancers and inorganic pore formers.
  • photocatalytic activity enhancers include a metal or metal oxide selected from the group consisting of Pt, Pd, Au, Os, Rh, RuO 2 , Nb, Cu, Sn, Ni, and Fe.
  • the combination of the photocatalytic particles with the noted metals or metal oxides can improve the photocatalytic activity.
  • Exemplary inorganic pore formers include calcium carbonate and aluminum trihydrate. Various combinations of such optional additives may be included.
  • an optional additive may be included in an amount of at least 1 wt-%, based on the total weight of the coating. In certain embodiments, an optional additive may be included in an amount of up to 10 wt-%, based on the total weight of the coating.
  • the photocatalytic coating on each base ceramic granule is at least 1 micrometer (micron) thick. In certain embodiments, the photocatalytic coating on each base ceramic granule is up to 20 microns thick. Such coating is not necessarily uniform or continuous.
  • the photocatalytic coating is formed from a coatable composition containing an inorganic binder and a plurality of photocatalytic particles, which is coated on previously uncoated (and typically unfired) base ceramic granules.
  • Such intermediate coated granules are heated at a temperature of at least 700°C to cure or sinter the base granule (if unfired) and produce a ceramic- type photocatalytic coating on the base granules.
  • Such firing temperatures are 300-400°C higher than that used for conventional granules.
  • the coatable composition is in the form of an aqueous slurry.
  • the aqueous slurry includes water in an amount of at least 30 percent by weight (wt-%), based on the total weight of the aqueous slurry.
  • the aqueous slurry includes solids in an amount of at least 10 wt-%, based on the total weight of the aqueous slurry. In certain embodiments, the aqueous slurry includes water in an amount of up to 90 wt-%, based on the total weight of the aqueous slurry. In certain embodiments, the aqueous slurry includes solids in an amount of up to 70 wt-%, based on the total weight of the aqueous slurry.
  • one or more dispersants may be added to the aqueous slurry to assist in dispersing the particles throughout the slurry.
  • the appropriate level of dispersion of particles in the slurry will assist in achieving a coating on the granules having a greater uniformity.
  • Both anionic and non-ionic dispersants may be suitable for use.
  • the dispersant is typically used in an amount of up to 5 wt-%, or up to 2 wt-%, based on the total weight of the particles.
  • An example of a dispersant is the sodium salt of sulfonated naphthalene-formaldehyde condensate marketed as RHODACAL N from Rhodia in Cranbury, NJ.
  • a coatable composition of the present disclosure is applied onto the uncoated ceramic granules to form a coating on the outer surface of the granules.
  • the term “coating” refers to one or more layers of coatings applied onto the granules.
  • the coating is preferably directed to the complete covering of the base granule, although this is not specifically required.
  • An exemplary process for coating the granules is generally disclosed in U.S. Pat. No.5,411,803 (George et al.).
  • the base ceramic granules may be initially preheated in a rotary kiln, or equivalent means, to a temperature of 65°C to 140°C. The coatable composition is then applied to uniformly coat the granules.
  • the photocatalytic coating is deposited on the base ceramic granules, which may be pre-fired or unfired, in a fluidized bed coater to achieve the desired thickness.
  • This coating method enables formation of a thin and uniform photocatalytic layer that affects the photocatalytic activity of the granule.
  • the rate of application for the coatable composition to an uncoated base ceramic granule may vary depending on the range of components within the composition and the capabilities of the equipment being used. Those skilled in the art are capable of determining this proper rate based upon the ranges described herein.
  • the heat of the granules drives off some of the water in the coatings to achieve a moisture level of 0.6% to 1%.
  • the intermediate coated granules (which may or may not include previously fired base granules) are then heated to temperatures necessary to provide insolubilization of the inorganic binders and thus form a ceramic coated inorganic granule.
  • the insolubilization of the binders renders the binders sufficiently resistant to dissolution in water or bituminous material.
  • the heating, or firing, of the intermediate coated granules takes place at temperatures of at least 700°C, and often up to 900°C.
  • the photocatalytic coated ceramic granules may optionally be post-treated to improve the handling of the material or to enhance the adhesion of the photocatalytic coated granules to other substrates.
  • Typical treatments may include, for example, hydrocarbon oils, silicones, and inorganic chemical solutions, such as solutions of magnesium chloride, and the like.
  • One useful silicone is known under the trade designation TEGOSIVIN HL15M7, an organosiloxane silicone oil, available from Goldschmidt Chemical, Hopewell, VA. Those skilled in the art are capable of determining the proper amount needed to achieve a desired result.
  • the additives are generally applied during the cooling step of the coating process.
  • Embodiment 1 is a plurality of photocatalytic coated ceramic granules comprising: base ceramic granules, each having an outer surface; and a photocatalytic coating disposed on the outer surface, wherein the photocatalytic coating comprises an inorganic binder and a plurality of photocatalytic particles selected from TiO 2 , ZnO, Ti(OH) 4 , doped derivatives thereof, and combinations thereof, wherein the photocatalytic particles have a surface area per weight of the particles of no more than 30 square meters per gram (m 2 /g); and wherein the photocatalytic coated ceramic granules have a Total Solar Reflectance (TSR) of at least 0.7.
  • TSR Total Solar Reflectance
  • Embodiment 2 is the coated ceramic granules of embodiment 1 having a TSR of at least 0.75, or at least 0.8.
  • Embodiment 3 is the coated ceramic granules of embodiment 1 or 2 wherein the photocatalytic particles have a surface area per weight of the particles of no more than 25 m 2 /g, no more than 20 m 2 /g, no more than 15 m 2 /g, no more than 14 m 2 /g, no more than 13 m 2 /g, no more than 12 m 2 /g, no more than 11 m 2 /g, or no more than 10 m 2 /g.
  • Embodiment 4 is the coated ceramic granules of any preceding embodiment wherein the photocatalytic particles have a surface area per weight of the particles of at least 1 m 2 /g.
  • Embodiment 5 is the coated ceramic granules of any preceding embodiment wherein the photocatalytic particles have a mean particle size of at least 100 nanometer (nm), and in certain embodiments, at least 200 nm, at least 500 nm, or at least 1000 nm.
  • Embodiment 6 is the coated ceramic granules of any preceding embodiment wherein the photocatalytic particles have a mean particle size of up to 3000 nm, up to 2000 nm, or up to 1000 nm.
  • Embodiment 7 is the coated ceramic granules of any preceding embodiment wherein the plurality of photocatalytic particles comprise TiO 2 (e.g., anatase TiO 2 ).
  • Embodiment 8 is the coated ceramic granules of any preceding embodiment wherein the inorganic binder in the photocatalytic coating comprises an alkali metal silicate binding agent.
  • Embodiment 9 is the coated ceramic granules of embodiment 8 wherein the alkali metal silicate binding agent is selected fyxm lithium silicate, potassium silicate, sodium silicate, and combinations thereof.
  • Embodiment 10 is the coated ceramic granules of embodiment 9 wherein the alkali silicate binding agent is selected from lithium silicate, potassium silicate, and combinations thereof.
  • Embodiment 11 is the coated ceramic granules of any preceding embodiment wherein the photocatalytic coating comprises a plurality of photocatalytic particles in an amount of at least 45 percent by weight (wt-%), or at least 60 wt-%, based on the total weight of the coating.
  • Embodiment 12 is the coated ceramic granules of any preceding embodiment wherein the photocatalytic coating comprises a plurality of photocatalytic particles in an amount of up to 95 wt-%, or up to 80 wt-%, based on the total weight of the coating.
  • Embodiment 13 is the coated ceramic granules of any preceding embodiment wherein the photocatalytic coating comprises an inorganic binder in an amount of at least 5 wt-%, at least 10 wt-%, at least 15 wt-%, or at least 20 wt-%, based on the total weight of the coating.
  • Embodiment 14 is the coated ceramic granules of any preceding embodiment wherein the photocatalytic coating comprises an inorganic binder in an amount of up to 55 wt-%, up to 50 wt- %, up to 45 wt-%, or up to 40 wt-%, based on the total weight of the coating.
  • Embodiment 15 is the coated ceramic granules of any preceding embodiment wherein the photocatalytic coating further comprises a crosslinker.
  • Embodiment 16 is the coated ceramic granules of embodiment 15 wherein the crosslinker is selected from boric acid, a borate, a silicate, a fluoroaluminate, an aluminosilicate, and combinations thereof.
  • Embodiment 17 is the coated ceramic granules of embodiment 15 or 16 wherein the photocatalytic coating comprises a crosslinker in an amount of at least 2 wt-%, based on the total weight of the coating.
  • Embodiment 18 is the coated ceramic granules of any of embodiments 15 through 17 wherein the photocatalytic coating comprises a crosslinker in an amount of up to 10 wt-%, based on the total weight of the coating.
  • Embodiment 19 is the coated ceramic granules of any preceding embodiment wherein the photocatalytic coating further comprises one or more optional additives selected from a photocatalytic activity enhancer, an inorganic pore former, and combinations thereof.
  • Embodiment 20 is the coated ceramic granules of embodiment 19 wherein the photocatalytic coating comprises one or more additives in an amount of at least 1 wt-%, based on the total weight of the coating.
  • Embodiment 21 is the coated ceramic granules of embodiment 19 or 20 wherein the photocatalytic coating comprises one or more additives in an amount of up to 10 wt-%, based on the total weight of the coating.
  • Embodiment 22 is the coated ceramic granules of any preceding embodiment wherein the photocatalytic coating on each base ceramic granule is at least 1 micron thick.
  • Embodiment 23 is the coated ceramic granules of any preceding embodiment wherein the photocatalytic coating on each base ceramic granule is up to 20 microns thick.
  • Embodiment 24 is the coated ceramic granules of any preceding embodiment wherein the base ceramic granules have a TSR of at least 0.7, at least 0.75, or at least 0.8.
  • Embodiment 25 is the coated ceramic granules of any preceding embodiment wherein the base ceramic granules comprise a plurality of ceramic particles.
  • Embodiment 26 is the coated ceramic granules of embodiment 25 wherein the base ceramic granules comprise a plurality of ceramic particles, an inorganic binder, and optionally a hardener.
  • Embodiment 27 is the coated ceramic granules of any preceding embodiment wherein the base ceramic granules comprise an inorganic core having an outer surface and a shell on and surrounding the outer surface.
  • Embodiment 28 is the coated ceramic granules of embodiment 27 wherein the inorganic core is a solid ceramic core.
  • Embodiment 29 is the coated ceramic granules of embodiment 27 wherein the inorganic core is at least one of a crystalline, a glass, or a glass-ceramic.
  • Embodiment 30 is the coated ceramic granules of any of embodiments 27 through 29 wherein the core has a diameter of at least 200 micrometers.
  • Embodiment 31 is the coated ceramic granules of any of embodiments 27 through 30 wherein the shell has a thickness of at least 50 micrometers, and in certain embodiments, up to 400 micrometers.
  • Embodiment 32 is the coated ceramic granules of any of embodiments 27 through 31 wherein the shell comprises ceramic particles bound together with an inorganic binder (i.e., a binder distinct from the photocatalytic coating binder, although these binders could be compositionally the same or similar).
  • Embodiment 33 is the coated ceramic granules of embodiment 32 wherein the shell comprises at least first and second concentric layers, wherein the first concentric shell layer is closer to the core than the second concentric shell layer, wherein the first concentric shell layer comprises ceramic particles bound together with an inorganic binder.
  • Embodiment 34 is the coated ceramic granules of embodiment 32 or 33 wherein the inorganic binder comprises a reaction product of at least an alkali silicate and a hardener.
  • Embodiment 35 is the coated ceramic granules of embodiment 34 wherein the hardener is amorphous.
  • Embodiment 36 is the coated ceramic granules of embodiment 34 or 35 wherein the hardener is selected from aluminum phosphate, an aluminosilicate, a cryolite, a calcium salt, a calcium silicate, and combinations thereof.
  • Embodiment 37 is the coated ceramic granules of any of embodiments 32 through 36 wherein the ceramic particles are present in an amount of greater than 50 wt-% of the shell of the respective base ceramic granule, based on the total weight of the shell of the respective base ceramic granule.
  • Embodiment 38 is the coated ceramic granules of any preceding embodiment wherein the ceramic particles of each base ceramic granule include no more than 10 wt-% TiO 2 , based on the total weight of either the core or base ceramic granule, for the respective core or base ceramic granule.
  • Embodiment 39 is the coated ceramic granules of any preceding embodiment wherein the ceramic particles of each base ceramic granule include no more than 10 wt-% Al 2 O 3 , based on the total weight of either the core or base ceramic granule, for the respective core or base ceramic granule.
  • Embodiment 40 is the coated ceramic granules of any preceding embodiment wherein the photocatalytic coating of the coated ceramic granules demonstrate photocatalytic activity of greater than 10 X 10 5 , or greater than 100 X 10 5 in relative TPA activity units.
  • Embodiment 41 is a method of making photocatalytic coated ceramic granules comprising base ceramic granules, each having an outer surface, and a photocatalytic coating disposed on the outer surface, the method comprising: providing a coatable composition containing an inorganic binder and a plurality of photocatalytic particles selected from TiO 2 , ZnO, Ti(OH) 4 , doped derivatives thereof, and combinations thereof, wherein the photocatalytic particles have a surface area per weight of the particles of no more than 30 square meters per gram (m 2 /g); applying the coatable composition to uncoated base ceramic granules to form intermediate coated granules; and heating the intermediate coated granules at a temperature of at least 700°C to produce the photocatalytic coated ceramic granules having a Total Solar Reflectance (TSR) of at least 0.7.
  • TSR Total Solar Reflectance
  • Embodiment 42 is the method of embodiment 41 wherein the coatable composition is an aqueous slurry, preferably comprises water in an amount of at least 30 wt-%, based on the total weight of the aqueous slurry.
  • Embodiment 43 is the method of embodiment 42 wherein the aqueous slurry further comprises a dispersant.
  • Embodiment 44 is the method of any of embodiments 41 through 43 wherein the uncoated base ceramic granules are unfired.
  • Embodiment 45 is the method of any of embodiments 41 through 44 wherein heating the intermediate coated granules occurs at a temperature of up to 900°C.
  • Ceramic base granules analogous to these industrially produced ceramic base granules can be made using the following procedure as well. Although the data presented in Table 3 for Example 3 and Comp Ex 2-3 are for the industrially produced ceramic base granules, it is believed that analogous data would result if the following procedure were used to produce them. Ceramic base granules were prepared by applying a thick reflective coating layer in a form of aqueous slurry on crushed mineral cores as follows: Grade #11 crushed uncoated naturally occurring dacite mineral (obtained from 3M Company, St. Paul, MN) was screened to 14 grade using -14 mesh U.S.
  • Aqueous slurries for forming the shell coating of a core-shell granule were formulated using raw materials listed in Table 2 taken in proportions (in grams) listed in Table 3 (referred to “Base Granules”).
  • the slurries were made generally as follows: Minex 4 and Metamax were combined with water to fabricate an aqueous slurry comprising about 60 wt-% of solids and milled in a vertical attrition mill until median particle size around 3.5 microns is reached. Next, the obtained slurry was combined with water and liquid silicate (“STAR”) resulting in a slurry of final formulation comprising 30.4 wt-% of solids. The final slurry was stirred vigorously and mixed via high shear using a Cowles blade at 500 revolutions per minute (rpm) for at least 15 minutes (min) and maintained in suspension via continuous stirring while being pumped into fluidized bed coater.
  • STAR liquid silicate
  • the slurry spray rate was kept as high as possible without accumulating moisture in the product bed.
  • Product temperature was kept in the range 26-32°C
  • the atomizing pressure was 20-35 pounds per square inch (psi) (138-241 kiloPascals (kPa))
  • the fluidizing air was 1000-1200 feet per minute (fpm) (5-6 meters per second (m/s)) and the spray rate was 25-40 grams per minute (g/min).
  • the fluidizing air was generally kept as low as possible while maintaining fluidized bed motion. Typical settings of batch fluid bed coater that was used as outlined below.
  • Solids starting charge grams (g) 1000-1300 Air velocity, 5-6 meters per second (mps) Process Temp setpoint, °C 60-80 Process Temp reading, °C 60-80 Product Temp, °C 25-30 Pressure Drop (D/P) across filter, range 50-100 D/P across material bed, range 50-150 Relative Humidity (R/H) in exhaust air, range, % 30-50 Atomizing air pressure, kPa 172-210
  • D/P Pressure Drop
  • R/H Relative Humidity
  • kPa 172-210 For a batch of 1-2 kilograms (kg) of core granules (i.e., the core of core-shell base granules), the coating process to form a shell coating of final thickness of approximately 300 micrometers took about 2-3 hours.
  • Final thickness of the first coating layer of Examples 1-3 and Comparative Examples ranged from 200 to 400 micrometers, which corresponded to about 50-85 wt-% of the whole granule construction.
  • Ceramic Granules for Comparative Example 1 were prepared as follows: the slurry components in the proportions (in grams) indicated in Table 3 were combined in a vertical mixer with 15 grams of additional water to prepare an aqueous slurry. The core granule substrate in the proportions (in grams) indicated in Table 3 was pre-heated to 90-95°C and then combined with the prepared aqueous slurry in a vertical or horizontal mixer. Grade #11 uncoated cores were used as the substrate for the base granule.
  • the slurry coated base granules were then fired in a rotary kiln (natural gas/oxygen flame) reaching the indicated temperature over a period of 10-20 min. Following the firing the granules were allowed to cool to room temperature.
  • the components and proportions (in grams) of the photocatalytic coating composition for Comparative Example 1 is listed in Table 3 were combined and coated on this fired base granule using the same method as the shell layer on the core granule substrate.
  • General Method of Applying Photocatalytic Coating The photocatalytic coating layer is designed as final thin layer (1-20 microns) applied in a fluidized bed coater on base granules of Examples 1-3 and Comparative Examples (Comp Ex 2-3) described above.
  • the components and proportions of such components (in grams) of the photocatalytic coating compositions are listed in Table 3.
  • the coating was applied in a lab-scale fluidized bed coater.
  • Aqueous slurries for coating were formulated using raw materials listed in Table 2 taken in proportions (in grams) listed in Table 3.
  • titania powders were suspended in water with silicate and boric acid solution. The slurries were constantly agitated during application at 100 rpm.
  • product temperature was kept in the range of 20-25°C, atomizing pressure 20-35 psi (138-241 kPa), fluidizing air 1000-1200 fpm (5-6 m/s) and spray rate 10-15 g/min.
  • the following refractive index values were used for the calculation: water (1.33) and TiO 2 (2.488).
  • the dispersion was diluted to approximately 1 wt-% solids with water.
  • the diluted sample was then added to the measurement cell which was filled with water until the transmittance was between the recommended levels of 85-95%.
  • a particle size distribution of D50 is also known as the median diameter of the particle size distribution. It is the value of the particle diameter at 50% in the cumulative distribution.
  • BET Brunauer, Emmett and Teller
  • Aqueous disodium terephthalate solution 500 g of 10 -4 M was then added to the dish. The mixture was stirred using a bar placed in a submerged small Petri dish and driven by a magnetic stirrer underneath the crystallization dish. The mixture was exposed to ultraviolet (UV) light produced by an array of 4, equally spaced, 4-ft (1.2-m) long black light bulbs (Sylvania 350 BL 40W F40/ 350BL).
  • UV ultraviolet
  • the height of the bulbs was adjusted to provide about 2.3 mW/cm 2 UV flux measured using a VWR Model 21800-016 UV Light Meter (VWR International, West Chester, PA) equipped with a UVA Model 365 Radiometer (Solar Light Company, Glenside, PA) having a wavelength band of 320- 390 nanometers (nm).
  • VWR Model 21800-016 UV Light Meter
  • UVA Model 365 Radiometer
  • nm nm
  • about 3 mL of the mixture was removed with a pipet at about 5-minute intervals and transferred to a disposable 4-window polymethylmethacrylate or quartz cuvette.
  • the mixture in the cuvette was then placed into a Fluoromax-3 spectrofluorometer (Jobin Yvon, Edison, NJ).

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
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Abstract

L'invention concerne plusieurs granulés céramiques à revêtement photocatalytique comprenant des granulés céramiques de base, ayant chacun une surface externe, et un revêtement photocatalytique disposé sur la surface externe. Le revêtement photocatalytique comprend un liant inorganique et plusieurs particules photocatalytiques choisies parmi TiO2, ZnO, TriOH4, des dérivés dopés associés et des combinaisons de ces éléments. Les particules photocatalytiques présentent une surface par poids de particules de pneus ne dépassant pas 30 mètres carrés par gramme (m2/g). Les granulés céramiques revêtus ont une réflectance solaire totale d'au moins 0,7.
PCT/IB2020/060671 2019-11-18 2020-11-12 Granulés céramiques à revêtement photocatalytique et leur procédé de fabrication WO2021099898A1 (fr)

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EP20821064.1A EP4062006B1 (fr) 2019-11-18 2020-11-12 Granulés céramiques à revêtement photocatalytique et leur procédé de fabrication
CN202080075632.8A CN114641598A (zh) 2019-11-18 2020-11-12 具有光催化涂层的陶瓷粒料及其制备方法
US18/408,421 US20240141649A1 (en) 2019-11-18 2024-01-09 Ceramic granules with a photocatalytic coating and method of making

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WO2024081290A1 (fr) * 2022-10-11 2024-04-18 U.S. Silica Company Compositions granulaires réfléchissantes

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